Production of salicylaldehydes



Un States 3,098,875 Patented July 23, 1963 of Delaware No Drawing. Filed July 5, 1960, Ser. No. 40,511 16 Claims. (Cl. 260-600) This application is a continuation-in-part of my copending applications Serial No. 707,691, filed January 8, 1-958, and 707,692, filed January 8, 1958, both now abandoned.

This invention relates to a process for the production of oxygenated organic compounds and particularly to a process for the preparation of aromatic aldehydes. More particularly the invention concerns a method for the production of aromatic aldehydes such as salicylaldehydes, said salicylaldehydes containing, if so desired, one or more alkyl substituents.

One object of this invention is to provide a process for preparing oxygenated aromatic compounds.

A further object of this invention is to provide a process for the production of aromatic aldehydes such as salicylaldehydes which may contain one or more alkyl substituents on the ring.

One embodiment of this invention resides in a process for the production of a salicylaldehyde which comprises heating a phenol, in which at least one carbon atom ortho to the hydroxy substituent is unsubstituted, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkylradicals containing from 1 to about 18 carbon atoms, with carbon monoxide and the corresponding phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres, treating the resultant product with an acid, and recovering the desired salicylaldehyde.

A further embodiment of the invention resides in a process for the production of a salicylaldehyde which comprises heating phenol with carbon monoxide and the corresponding phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres, treating the resultant product with an acid and recovering the desired salicylaldehyde.

A specific embodiment of the invention resides in a process for the preparation of S methylsalicylaldehyde which comprises heating p-cresol with carbon monoxide and sodium p-methylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres, treating the resultant product with a dilute inorganic acid and recovering the desired S-methylsalicylaldehyde.

Other objects and embodiments referring to alternative phenolic compounds and to alternative phenoxides will be found in the following further detailed description of the invention.

The aromatic oxygenated compounds and particularly the aromatic aldehydes such as salicylaldehyde which may contain alkyl substituents on the nucleus which are prepared according to the process of this invention will find a wide variety of uses in the chemical field. For example, the alkylsalicylaldehydes may be used as intermediates in the preparation of copper deactivators, which are additives in gasoline, one advantage of the deactivators thus formed being that they are in a liquid state rather than in a crystalline state and will thus be relatively more soluble in the gasoline or petroleum product than the deactivators which are prepared in the solid state. In addition, salicylaldehyde thus formed may also be used as an intermediate in the preparation of acetylsalicylic acid, a well-known medicine, or it may also be used as an intermediate in the preparation of other pharmaceuticals.

Heretofore, it was known that aromatic hydrocarbons such as benzene could be treated with carbon monoxide in the presence of a metal halide to form an aldheyde such as benzaldehyde. This reaction is essentially a Friedel-Crafts acylation, the reaction being one in which a formyl halide such as formyl chloride is formed as an intermediate and condenses with the aromatic hydrocarbon to yield an aldehyde. However, the present invention concerns the treatment of a hydroxy substituted compound such as a phenolic compound which may contain alkyl substituents on the ring, the only requirement which the starting material must have being that one of the carbon atoms ortho to the hydroxy substituent be free of any substituents.

Hydroxy substituted aromatic compounds which may be used in the process of this invention include phenol, as well as alkyl substituted phenols such as o-cresol, mcresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, other butylphenols, pentylphenols, hexylphenols, heptylphenols, oc-. tylphenols,nonylphenols, decylphenols, undecylphenols, dodecylphenols, tridecylphenols, tetradecylphenols, pentadecylphenols, hexadeoylphenols, heptadecylphenols, octadecylphenols, etc., 2,3-dimethylphenol, 2,4-dimethylphencl, 2,5-dimethylphenol, 3,4dimethylphenol, 3,5-dimeth ylphenol, 2,3-diethylphenol, 2,4-diethylphenol, 2,5-diethylphenol, 3,4-diethylphenol, 3,5-diethylphenol, 2,3-dipropylphenols, 2,4-dipropylphenols, 2,5-dipropylphenols, 3,4- dipropylphenols, 3,5-dipropylphenols, etc.

i The novel catalysts as used in the present invention include aluminum phenoxides such as aluminum phenoxide, aluminum o-cresoxide (aluminum o-methylphenoxide), aluminum m-cresoxide (aluminum m-methylphenoxide), aluminum p-cresoxide (aluminum p-methylphenoxide), aluminum o-ethylphenoxide, aluminum m-ethylphenoxide, aluminum p-ethylphenoxide, aluminum o-propylphenoxides, aluminum m-propylphenoxides, aluminum ppropylphenoxides, aluminum o-butylphenoxides, aluminum m-butylphenoxides, aluminum p-butylphenoxides, aluminum pentylphenoxides, aluminum hexylphenoxides, aluminum heptylphenoxides, aluminum octylphenoxides, aluminum nonylphenoxides, aluminum decylphenoxides, aluminum undecylphenoxides, aluminum dodecylphenoxides, aluminum tridecylp-henoxides, aluminum tetradecylphenoxides, aluminum pentadecylphenoxides, aluminum hexadecylphenoxides, aluminum heptadecylphen oxides, aluminum octadecylphenoxides, aluminum 2,3-dimethylphenoxide, aluminum 2,4-dimethylphenoxide, aluminum 2,5-dimethylphenoxide, aluminum 3,4-dimethylphenoxide, aluminum 3,5-dimethylphenoxide, aluminum 2,3-diethylphenoxide, aluminum 2,4-diethylphenoxide, aluminum 2,5-diethylphenoxide, aluminum 3,4-diethylphenoxide, aluminum 3,5-diethylphenoxide, aluminum 2,3-dipropylphenoxides, aluminum 2,4-dipropylphenoxides, aluminum 2,5-dipropylphenoxides, aluminum 3,4-dipropylphenoxides, aluminum 3,5-dipropylphenoxides, aluminum 2,3-dibutylphenoxides, aluminum 2,4-dibutylphenoxides, aluminum 2,5-dibutylphenoxides, aluminum 3,4-dibutylphenoxides, aluminum 3,5-dibutylphenoxides, aluminum 2,5- and 3,5-dipentyl-, dihexyl-, diheptyl-, diocty1-, dinonyl-, didecyl-, diundecyl-, didodecyl-, ditridecyl-, ditetradecy1-, dipentadecyh, dihexadecyl-, diheptadecyl-, dioctadecylphenoxides, etc.; alkali metal phenoxides and alkaline earth metal phenoxides such as sodium phenoxide, lithium phenoxide, potassium phenoxide, magnesium phenoxide, calcium phenoxide, sodium o-, mand p-cresoxide, lithium o-, mand p-cresoxide, magnesium o-, mand p-cresoxide, calcium o-, mand p-cresoxide, sodium o-, mand pethylphenoxide, lithium o-, mand p-ethylphenoxide, potassium o, mand p-ethylphenoxide, magnesium mand .p-ethylphenoxide, calcium o-, mand p-ethylphenoxide, sodium o-, mand p-propylphenoxides, lithium o-, mand p-propylphenoxides, potassium o-, mand p-propylphenoxides, magnesium o-, mand p-propylphenoxides, calcium o-, mand p-propylphenoxides, sodium o-, mand p-butylphenoxides, sodium o-, mand p-pentylphenoxides, lithium o-, mand p-pentylp-henoxides, potassium o-, mand p-pentylphenoxides, magnesium o-, mand p-penty-lphenoxides, calcium o-, mand p-pentylphenoxides, etc. It is also contemplated Within the scope of this invention that the rubidium, cesium, strontium and barium phenoxides and the aforementioned alkyl substituted phenoxides may also be employed as well as the higher molecular weight alkyl substituted phenoxides such as the alkali metal and alkaline earth metal o-, mand p-hexylphenoxides, heptylphenoxides, octylphenoxides, nonpylphenoxides, decylphenoxides, undecylphenoxides, dodecylphenoxides, tridecylphenoxides, tetradecylphenoxides, pentadecylphenoxides, hexadecylphenoxides, heptadecylphenoxides, octadecylphenoxides, etc. Other phenoxides which may also be employed include sodium, potassium, lithium, rubidium, cesium, magnesium, calcium, strontium, and barium dialkyl substituted phenoxides such as sodium 2,3-dimethylphenoxide, potassium 2,3- dimethylphenoxide, magnesium 2,3-dimethylphenoxide, calcium 2,3-dimethylphenoxide, sodium 2,4-dimethylphenoxide, potassium 2,4-dimethylphenoxide, magnesium 2,4- dimethylphenoxide, calcium 2,4-dimet-hyl phenoxide, sodium 2,4-dimethylphenoxide, potassium 2,5-dimethylphenoxide, magnesium 2,5-dimethylphenoxide, calcium 2,5- dimethylphenoxide, sodium 2,3-diethylphenoxide, potassium 2,3-diethylphenoxide, magnesium 2,3-diethylphenoxide, calcium 2,3-diethylphenoxide, sodium 3,4-diethylphenoxide, potassium 3,4-diethylphenoxide, magnesium 3,4-diethylphenoxide, calcium 3,4-diethylphenoxide, sodium 3,4-dibutylphenoxides, potassium 3,4-dibutylphenoxides, magnesium 3,4-dibutylphenoxides, calcium 3,4-dibutylphenoxides, sodium 3,4-dibutylphenoxides, potassium 3,5-dibutylphenoxides, magnesium 3,5-dibutylphenoxides, calcium 3,5-dibutylphenoxides, etc. It is to be understood that the process of the present invention is not necessarily limited to the alkali metal or alkaline earth metal phenoxides hereinbefore set forth, but that other of said phenoxides may also 'be employed, however, not necessarily with equivalent results.

In a preferred embodiment of the invention the reactants comprising the hydroxy substituted aromatic compound, the particular phenoxide, either an aluminum phenoxide, an alkali metal phenoxide or an alkaline earth metal phenoxide and the carbon monoxide are usually condensed using an approximately equimolar amount of each of the phenolic compounds and an excess of carbon monoxide. However, a molar excess of the phenolic or hydroxy substituted aromatic compound over the particular aluminum-, alkali metal or alkaline earth metal phenoxide may be employed, the particular phenoxide acting as a catalyst for the reaction involving the excess phenolic compound. The reaction will take place at an elevated temperature usually in the range of from about 100 to about 350 C. or more and preferably in a range of from about 200 to about 300 C. In addition, the reaction is also carried out at pressures ranging from about atmospheric to about 300 atmospheres or more, and preferably in a range of from about 40 atmospheres to about 150 atmospheres or more, the particular pressure being dependent upon the reactants used and the temperatures em- 4 ployed, sufficient pressure being used to maintain a portion of the reactants in the liquid phase.

It is also contemplated within the scope of this invention that the present process, if so desired, may be effected in the presence of an inert organic solvent or diluent. Suitable diluents which may be used include aromatic hydrocarbons such as benzene, toluene, o-xylene, mxylene, p-xylene, ethylbenzene, etc.; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, etc.; ethers such as dimethyl ether, diethyl ether, dipropyl ether, etc.; saturated low molecular weight aliphatic hydrocarbons such as pentane, hexane, heptane, etc.; saturated cyclic hydrocarbons such as cyclopentane, cyclohexane, methyloyclopentane, methylcyclohexane, etc.; or acetone, acetic acid, etc.

Following the reaction between the phenolic compound, the carbon monoxide and the particular phenoxide the reaction product may then be treated with water and/or a diluent acid such as dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, dilute phosphoric acid, etc., to decompose the thus formed aluminum, alkali metal or alkaline earth metal compound and recover the desired salicylaldehyde which has been formed.

The process of this invention may be effected in any suitable manner and may comprise either a batch or a continuous type operation. For example, when a batch type operation is used a quantity of the hydroxy substituted aromatic compound and the corresponding phenoxide is placed in an appropriate apparatus which may comprise a rotating autoclave or other suitable equipment. The apparatus is sealed and carbon monoxide is pressured in until the desired pressure has been reached after which the apparatus is heated to the desired temperature and maintained thereat for a predetermined residence time. At the end of this time the apparatus and contents thereof are cooled to room temperature, the excess pressure is vented, the reaction product may be treated with water and/or dilute acid to decompose the aluminum, alkali metal or alkaline earth metal compound, and the desired salicylaldehyde or alkyl substituted salicyl-aldehyde is separated and recovered by conventional means such as, fractional distillation, crystallization, etc.

Another type of operation which may be used, which constitutes the preferred operation of the present invention, is a continuous method in which the hydroxy substituted aromatic compound and the corresponding aluminum, alkali metal or alkaline earth metal phenoxide are continuously charged to a reaction zone which is maintained at the proper operating conditions of temperature and pressure. These reactants may be charged through separate lines or, if so desired, they may be admixed prior to entry into said reactor and charged thereto in a single stream. In addition, the carbon monoxide is also continuously charged to said reaction zone through a separate line. After a predetermined residence time in the reaction zone, which may constitute an unpacked vessel or coil or which may be lined with an adsorbent packing material such as dehydrated bauxite, fire brick, alumina and the like, the reaction product is continuously withdrawn and separated from the reactor efiiuent, the latter being separated and recycled to form a portion of the feed material, while the former is purified by conventional means hereinbefore set forth.

The following examples are given to illustrate the process of the present invention which, however, are not intended to limit the generally broad scope of the present invention in strict accordance therewith.

Example I A mixture of g. of phenol and 300 g. of aluminum phenoxide is placed in the glass liner of a rotating autoclave. The liner is then sealed into the autoclave and carbon monoxide is pressed in until a pressure of 100 atmospheres has been reached. The autoclave and contents thereof are then heated to a temperature of about 200 C. and maintained at this temperature for a period of approximately 6 hours. At the end of this time the autoclave and contents thereof are cooled to room temperature, the excess pressure is vented and the reaction product is boiled with water, then ether extracted, and the extract is subjected to fractional distillation, the cut boiling at l95-l97 C. at 760 mm. pressure, comprising salicylaldehyde, is separated and recovered.

Example II One hundred grams of p-cresol and 30 g. of aluminum p-cresoxide are placed in the glass liner of a rotating autoclave which is thereafter sealed into the autoclave. Carbon monoxide is pressed in until a pressure of about 150 atmospheres is reached, after which the autoclave and contents thereof are heated to a temperature of about 200 C. The autoclave is maintained at this temperature for a period of about 6 hours at the end of which time it is allowed to cool to room temperature. The excess pressure is vented and the reaction product after being boiled with water and ether extracted is subjected to fractional distillation, the cut consisting of S-methylsal-icylaldehyde being separated and recovered therefrom.

Example 111 A mixture of o-ethy-lphenol and aluminum o-ethylphenoxide is subjected to the same treatment as described in Example I above. The reaction product resulting from the reaction is subjected to fractional distillation and the desired compound, comprising 3-ethylsalicylaldehyde is separated and recovered.

Example IV In a manner similar to that described in Example II above a mixture of o-cresol and aluminum o-cresoxide is subjected to treatment with carbon monoxide at an elevated temperature and pressure. The desired product, comprising 3-methylsalicylaldehy-de, is separated and recovered by fractional distillation from the reaction product.

Example V A mixture of 100 g. of p-butylphenol and 20 g. of aluminum p-butylphenoxide is placed in a rotating autoclave which is sealed and carbon monoxide pressed in until a pressure of 100 atmospheres has been reached. The autoclave is heated to a temperature of about 250 C. and maintained thereat for a period of about 6 hours. At the end of this time the autoclave and contents thereof are cooled to room temperature, the excess pressure is vented and the reaction product is recovered. The reaction product is boiled with water, ether extracted and the extract is subjected to fractional distillation, the cut consisting of S-butylsalicylaldehyde being separated and recovered therefrom.

Example VI A mixture of 200 g. of phenol and 200 g. of sodium phenoxide is placed in the glass liner of a rotating autoclave. The liner is then sealed into the autoclave and carbon monoxide is pressed in until a pressure of 120 atmospheres has been reached. The autoclave and contents thereof are then heated to a temperature of about 200 C. and maintained at this temperature for a period of approximately 6 hours. At the end of this time the autoclave and contents thereof are cooled to room temperature, the excess pressure is vented and the reaction product is treated with dilute sulfuric acid, ether extracted and the extract is subject to fractional distillation, the cut boiling at l95-l97 C. at 760 mm. pressure, comprising salicylatldehyde, is separated and recovered.

Example VII One hundred grams of p-cresol and 20 g. of lithium pcresoxide are placed in a glass liner of a rotating autoclave which is thereafter sealed iIlItO the autoclave. Carbon monoxide is pressed in until a pressure of about 100 atmospheres is reached, after which the autoclave and contents thereof are heated to a temperature of about 200 C. The autoclave is maintained at this temperature for a period of about 6 hours at the end of which time it is allowed to cool to room temperature. The excess pressure is vented and the reaction product is subjected to fractional distillation, the cut consisting of 5- methylsalicylaldehyde being separated and recovered therefrom.

Example VIII A mixture of o-ethylphenol and magnesium o-ethylphenoxide is subjected to the same treatment as described in Example I above. The reaction product resulting from the reaction is subjected to fractional distillation and the desired compound, comprising 3-ethylsalicylaldehyde is separated and recovered.

Example IX In a manner similar to that described in Example VII above a mixture of p-cnesol and potassium p-cresoxide is subjected to treatment with carbon monoxide at an elevated temperature and pressure. The desired product, comprising S-methylsalicylaldehyde, is separated and recovered 'by fractional distillation from the reaction product.

Example X A mixture of g. of p-butylphenol and 30 g. of calcium p-butylphenoxide is placed in a rotating autoclave which is sealed and carbon monoxide pressed in until a pressure of 100 atmospheres has been reached. The autoclave is heated to a temperature of about 250 C. and maintained thereat for a period of about 8 hours. At the end of this time the autoclave and contents thereof are cooled to room temperature, the excess pressure is vented and the reaction product is recovered. The reaction product is subjected to fractional distillation, the cut consisting of S-butylsalicylaldehyde being separated and recovered therefrom.

Example XI A mixture of 100 g. of p-cresol and 20 g. of sodium p-methylphenoxide (p-cresoxide) is placed in the glass liner of a rotating autoclave which is thereafter sealed into said autoclave. Carbon monoxide is pressed in until a pressure of about 100 atmospheres is reached, after which the autoclave and contents thereof are heated to a temperature of about 200 C. The autoclave is maintained at this temperature for a period of about 6 hours at the end of which time it is allowed to cool to room temperature. The excess pressure is vented and the reaction product is treated with dilute sulfuric acid, the resulting solution is extracted with ether and the extract is subjected to fractional distillation, the cut consisting of S-methylsalicylaldehyde being separated and recovered therefrom.

Example XII A mixture of 100 g. of p-dodecylphenol and 100 g. of potassium p-dodecylphenoxide is placed in the glass liner of a rotating autoclave which is thereafter sealed into the autoclave. Carbon monoxide is pressed in until a pressure of about 100 atmospheres is reached after which the autoclave and contents thereof are heated to a temper: ature of about 200 C. Upon completion of the desired reaction time which is approximately 6 hours the autoclave and contents thereof are cooled to room temperature. The excess pressure is vented and the reaction product is treated with dilute hydrochloric acid. Following this the solution is extracted with ether and the ether extract is subjected to fractional distillation under reduced pressure, the cut comprising S-dodecylsalicylaldehyde being separated and recovered therefrom.

Example XIII In this example a mixture of p-octadecylphenol and sodium p-octadecylphenoxide is subjected to the same treatment as described in the above examples. The reaction product resulting from the treatment with carbon monoxide at elevated temperatures and pressures is treated with dilute nitric acid, the solution is extracted with ether and the ether extract is subjected to fractional distillation, the desired reaction product comprising S-octadecylsalicylaldhyde being separated and recovered.

I claim as my invention:

1. A process for the production of a salicylaldehyde compound selected from the group consisting of salicylaldehyde and alkyl salicylaldehydes which comprises heating a phenol, in which at least one carbon atom ortho to the hydroxy substituent has hydrogen attached thereto, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkyl radicals containing from 1 to about 18 carbon atoms, with carbon monoxide and a phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides, at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufiicient time to form the desired salicylaldehyde compound, and recovering the last-mentioned compound.

2. A process for the production of salicylaldehyde which comprises heating phenol with carbon monoxide and a phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides, at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired salicylaldehyde, and recovering the lastmentioned compound.

3. A process for the production of S-methyl salicylaldehyde which comprises heating p-cresol with carbon monoxide and a phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides, at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired -methyl salicylaldehyde, and recovering the last-mentioned compound.

4. A process for the production of 3-ethyl salicylalde hyde which comprises heating o-rethylphenol with carbon monoxide and a phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides, at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired 3-ethyl salicylaldehyde, and recovering the llast-mentioned compound.

5. A process for the production of 5-dodecyl salicylaldehyde which comprises heating p-dodecylphenol with carbon monoxide and a phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides, at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a suflicient time to form the desired 5-dodecyl salicylaldehyde, and recovering the last-mentioned compound.

6. A process for the production of 5-octadecyl salicyl aldehyde which comprises heating p-octadecylphenol with carbon monoxide and a phenoxide selected from the group consisting of alkali metal phenoxides, alkaline earth metal phenoxides and aluminum phenoxides, at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a suificient time to form the desired 5-octadecyl salicylaldehyde, and recovering the last-mentioned compound.

7. A process for the production of a salicylaldehyde compound selected from the group consisting of salicylaldehyde and alkyl salicylaldehydes which comprises heating a phenol in which at least one carbon atom ortho to the hydroxy substituent has hydrogen attached thereto, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkyl radicals containing from 1 to about 18 carbon atoms, with carbon monoxide and aluminum phenoxide at a temperature in the range of from about to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufiicient time to form the desired sallicylaldehyde compound.

8. A process for the production of a salicylaldehyde compound selected from the group consisting of salicylaldehyde and alkyl salicylaldehydes which comprises heating a phenol in which at least one carbon atom ortho to the hydroxy substituent has hydrogen attached thereto, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkyl radicals containing from 1 to about 18 carbon atoms, with carbon monoxide and sodium p-rnethylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired salicylaldehyde compound, and recovering the last-mentioned compound.

9. A process for the production of a salicylaldehyde compound selected from the group consisting of salicyl aldehyde and alkyl salicylaldehydes which comprises heating a phenol in which at least one carbon atom ortho to the hydroxy substituent has hydrogen attached thereto, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkyl radicals containing from 1 to about 18 carbon atoms, with carbon monoxide and magnesium o-ethylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired salicylaildehyde compound, and recovering the last-rrrentioned compound.

10. A process for the production of a salicylaldehyde compound selected from the group consisting of salicylaldehyde and alkyl salicylaldehydes which comprises heating a phenol in which at least one carbon atom ortho to the hydroxy substituent has hydrogen attached thereto, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkyl radicals containing from 1 to about 18 carbon atoms, with carbon monoxide and potassium p-dodecylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufiicient time to form the desired salicylaldehyde compound, and recovering the last-mentioned compound.

M. A process for the production of a salicylaldehyde compound selected from the group consisting of salicylaldehyde and alkyl salicylaldehydes which comprises heating a phenol in which at least one carbon atom ortho to the hydroxy substituent has hydrogen attached thereto, selected from the group consisting of phenol and monoalkyland dialkylphenols, said alkyl radicals containing from 1 to about 18 carbon atoms, with carbon monoxide and sodium p-octadecylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a suflicient time to form the desired salicylaldehyde compound, and recovering the l-ast-mentioned compound.

12. A process for the production of salicylaldehyde which comprises heating phenol with carbon monoxide and aluminum phenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufiicient time to form the desired salicylaldehyde, and recovering the lastmentioned compound.

13. A process for the preparation of S-methyl-salicylaldehyde which comprises heating p-cresol with carbon monoxide and 'sodium p-methylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired S-methylsalicylaldehyde, and recovering the last-mentioned compound.

14. A process for the production of 3-ethy1sa1icyla1dehyde which comprises heating o-ethylphenol with carbon monoxide and magnesium o-ethylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired 3-ethy1salicylaldehyde, and recovering the last-mentioned compound.

15. A process for the production of S-dodecylsalicylaldehyde which comprises heating p-dodecyiphenol with carbon monoxide and potassium p-dodecylphenoxide at a temperature in the range of from about 100 to about 350 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufficient time to form the desired 5-dodecy1- salicylaldehyde, and recovering the last-mentioned compound.

d6. A process for the pnoduction of S-hexadecylsalicylaldehyde which comprises heating p-octadecylphenoi with carbon monoxide and sodium p-octadecylphenoxide at a temperature in the range of from about 100 to about 35 0 C. and at a pressure in the range of from about atmospheric to about 300 atmospheres in a proportion and for a sufiicient time to form the desired 5-octadecylsa1icy1- aldehyde, and recovering the last-mentioned compound.

No references cited. 

1. A PROCESS FOR THE PRODUCTION OF A SALICYLALDEHYDE COMPOUND SELECTED FROM THE GROUP CONSISTING OF SALICYLALDEHYDE AND ALKYL SALICYLALDEHYDES WHICH COMPRISES HEATING A PHENOL, IN WHICH AT LEAST ONE CARBON ATOM ORTHO TO THE HYDROXY SUBSTITUENT HAS HYDROGEN ATTACHED THERETO, SELECTED FROM THE GROUP CONSISTING OF PHENOL AND MONOALKYL- AND DIALKYLPHENOLS, SAID ALKYL RADICALS CONTANING FROM 1 TO ABOUT 18 CARBON ATOMS, WITH CARBON MONOXIDE AND A PHENOXIDE SELECTED FROMTHE GROUP CONSISTING OF ALKALI METAL PHENOXIDES, ALKALINE EARTH METAL PHENOXIDES AND ALUMINUM PHENOXIDES, AT A TEMPERATURES IN THE RANGE OF FROM ABOUT 100* TO ABOUT 350* C. AND AT A PRESSURE IN THE RANGE OF FROM ABOUT ATMOSPHERIC TO ABOUT 300 ATMOSPHERES IN A PROPORTION AND FOR A SUFFICIENT TIME TO FORM THE DESIRED SALICYLALDEHYDE COMPOUND, AND COVERING THE LAST-MENTIONED COMPOUND. 